EP3947622B1 - Procédé de fabrication d'un granulé ou d'une poudre - Google Patents

Procédé de fabrication d'un granulé ou d'une poudre Download PDF

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Publication number
EP3947622B1
EP3947622B1 EP20711944.7A EP20711944A EP3947622B1 EP 3947622 B1 EP3947622 B1 EP 3947622B1 EP 20711944 A EP20711944 A EP 20711944A EP 3947622 B1 EP3947622 B1 EP 3947622B1
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EP
European Patent Office
Prior art keywords
acid
powder
alkali metal
granule
chelating agent
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EP20711944.7A
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German (de)
English (en)
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EP3947622A1 (fr
Inventor
Frank Jaekel
Michael Klemens Mueller
Astrid Schmidt
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention is directed towards a process making a powder or granule containing
  • WO 2012/168739 a process is disclosed wherein slurries of complexing agents are spraydried under non-agglomerating conditions.
  • WO2015121170 A1 discloses a process for making a powder or granule containing 80 to 99% by weight of at least one chelating agent selected from MGDA, GLDA and IDS.
  • ADW formulations contain up to 40% of MGDA builder and are packaged in single unit doses, in brief also "SUD".
  • SUD single unit doses
  • the inventive process is a process for making a powder or granule, said powders and granules also being referred to as inventive powders and inventive granules, respectively.
  • the term "powder” refers to particulate materials that are solids at ambient temperature and that preferably have an average particle diameter in the range of from 1 ⁇ m to less than 0.1 mm, preferably 30 ⁇ m up to 75 ⁇ m.
  • the average particle diameter of inventive powders can be determined, e.g., by LASER diffraction methods, for example with Malvern apparatus, and refers to the volume average.
  • granule in the context of the present invention refers to particulate materials that are solids at ambient temperature and that preferably have an average particle diameter (D50) in the range of from 0.1 mm to 2 mm, preferably 0.4 mm to 1.25 mm, even more preferably 400 ⁇ m to 1 mm.
  • D50 average particle diameter
  • inventive granules can be determined, e.g., by optical or preferably by sieving methods.
  • Sieves employed may have a mesh in the range of from 60 to 3,000 ⁇ m.
  • Powders or granules made by the inventive process contain at least 75% by weight of chelating agent (A).
  • the contents of chelating agent (A) may be determined, e.g., by potentiometric titration with FeCl 3 .
  • the percentage refers to the solids content of said powder or granule and may be determined by Karl-Fischer titration or by drying at 160 to 200°C to constant weight with infrared light. It excludes crystal water.
  • Particles of powders and granules made by the inventive process may have regular or irregular shape.
  • Preferred shapes of particles of powders and of granules made by the inventive process are spheroidal shapes.
  • Alkali metal salts of GLDA are selected from compounds according to general formula (I b) [OOC-CH 2 CH 2 C-CH(COO)-N(CH 2 -COO) 2 ]M a-x H x (I b) wherein
  • alkali metal salts of MGDA are selected from lithium salts, potassium salts and preferably sodium salts of MGDA.
  • MGDA can be partially or preferably fully neutralized with the respective alkali.
  • an average of from 2.7 to three COOH groups of MGDA is neutralized with alkali metal, preferably with sodium.
  • chelating agent (A) is the trisodium salt of MGDA.
  • MGDA and its respective alkali metal salts are selected from the racemic mixtures, the D-isomers and the L-isomers, and from mixtures of the D- and L-isomers other than the racemic mixtures.
  • MGDA and its respective alkali metal salts are selected from the racemic mixture and from mixtures containing in the range of from 55 to 85 mole-% of the L-isomer, the balance being D-isomer.
  • Particularly preferred are mixtures containing in the range of from 60 to 80 mole-% of the L-isomer, the balance being D-isomer.
  • Other particularly preferred embodiments are racemic mixtures.
  • GLDA and its respective alkali metal salts are selected from the racemic mixtures, the D-isomers and the L-isomers, and from mixtures of the D- and L-isomers other than the racemic mixtures.
  • GLDA and its respective alkali metal salts are selected from the racemic mixture and from mixtures containing in the range of from 55 to 99 mole-% of the L-isomer, the balance being D-isomer.
  • Particularly preferred are mixtures containing in the range of from 60 to 98.5 mole-% of the L-isomer, the balance being D-isomer.
  • Other particularly preferred embodiments are racemic mixtures.
  • IDS and its respective alkali metal salts are selected from various mixtures of isomers, for example D,D-IDS, L,L-IDS and D,L-IDS and combinations therefrom. Preferred are optically inactive mixtures since they are cheaper to be manufactured.
  • alkali metal salt of chelating agent (A) may contain one or more impurities that may result from the synthesis of the respective chelating agent (A).
  • impurities may be selected from propionic acid, lactic acid, alanine, nitrilotriacetic acid (NTA) or the like and their respective alkali metal salts.
  • NTA nitrilotriacetic acid
  • impurities may be selected from maleic acid, monoamides of maleic/fumaric acid, and racemic asparagine. Such impurities are usually present in minor amounts.
  • a combination alkali metal salts of at least two different chelating agents is used, for example sodium salts of MGDA and GLDA in a weight ratio of from 1:1 to 5:1.
  • alkali metal salts of only one chelating agent is used, in particular sodium metal salts of MGDA.
  • Particles of powders or granules made by the inventive process further contain (B) at least one alkali metal silicate, hereinafter also referred to as alkali metal silicate (B).
  • alkali metal silicate refers to compounds comprising SiO 2 and M 2 O, having a molar ratio from 1.0 to 3.5, wherein M is an alkali metal, preferably potassium and/or sodium, more preferably sodium.
  • alkaline silicate such as sodium silicate or potassium silicate.
  • Alkali metal silicate are soluble in water and are generally manufactured by digestion of silica sand in an aqueous alkaline medium such as NaOH or KOH solution or by dissolving silicate glass, made from the fusion of sand and soda ash or potash, in water.
  • alkali metal silicate (B) is the sodium salt of water glass.
  • Particles of powders or granules made by the inventive process further contain (C) at least one (co)polymer containing carboxylic acid group, partially neutralized with alkali, hereinafter also referred to as (co)polymer (C) or, specifically, polymer (C) or copolymer (C), respectively.
  • Suitable comonomers for copolymers (C) are ethylenically unsaturated compounds, such as styrene, isobutene, ethylene, ⁇ -olefins such as propylene, 1-butylene, 1-hexene, and ethylenically unsaturated dicarboxylic acids and their alkali metal salty and anhydrides such as but not limited to maleic acid, fumaric acid, itaconic acid disodium maleate, disodium fumarate, itaconic anhydride, and especially maleic anhydride.
  • Suitable comonomers are C 1 -C 4 -alkyl esters of (meth)acrylic acid, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate.
  • (co)polymer (C) is selected from copolymers of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule. Comonomers bearing at least one sulfonic acid group per molecule may be incorporated into copolymer (C) as free acid or least partially neutralized with alkali.
  • Particularly preferred sulfonic-acid-group-containing comonomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide,
  • Useful copolymers (C) are, for example, random copolymers of acrylic acid and methacrylic acid, random copolymers of acrylic acid and maleic anhydride, ternary random copolymers of acrylic acid, methacrylic acid and maleic anhydride, random or block copolymers of acrylic acid and styrene, random copolymers of acrylic acid and methyl acrylate. More preferred are homopolymers of methacrylic acid. Even more preferred are homopolymers of acrylic acid.
  • (co)polymer (C) has an average molecular weight M w in the range of from 1,200 to 30,000 g/mol, preferably from 2,500 to 15,000 g/mol and even more preferably from 3,000 to 10,000 g/mol, determined by gel permeation chromatography (GPC) and referring to the respective free acid.
  • (Co)polymer (C) is partially neutralized with alkali, for example with lithium or potassium or sodium or combinations of at least two of the forgoing, especially with sodium.
  • alkali for example with lithium or potassium or sodium or combinations of at least two of the forgoing, especially with sodium.
  • in the range of from 10 to 95 mol-% of the carboxyl groups of (co)polymer (C) may be neutralized with alkali, especially with sodium, preferably in the range from 20-70 mole-% of the carboxyl groups, even more preferred in the range of from 25-60 mole-%.
  • copolymer (C) is selected from a combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule, both polymers being partially neutralized with alkali.
  • (co)polymer (C) is selected from sodium salts of polyacrylic acid with an average molecular weight M w in the range of from 1,200 to 30,000 g/mol, preferably from 2,500 to 15,000 g/mol and even more preferably from 3,000 to 10,000 g/mol, determined by gel permeation chromatography (GPC) and referring to the respective free acid.
  • M w average molecular weight
  • the weight ratio of (A):[(B) + (C)] is in the range of from 20 : 1 up to 100:1,
  • the weight ratio of (B)/(C) is in the range of from 10:1 to 1:10, preferably 1:1 to 1:5.
  • the inventive process comprises steps (a) and (b),
  • a solution of chelating agent (A) is provided that has a temperature of 35 to 50°C, and an aqueous solution of alkali metal silicate (B) is being added and (co)polymer (C), in bulk or in solution.
  • Step (a) can be performed at ambient temperature. In other embodiments, step (a) is being performed at 20° C or at elevated temperature, for example at a temperature in the range of from 25 to 90°C, preferably 60 to 75°C.
  • the water used in step (a) may be present in an amount that all chelating agent (A) and alkali metal silicate (B) and (co)polymer (C) are dissolved. However, it is also possible to use less amounts of water and mix chelating agent (A) and alkali metal silicate (B) and (co)polymer (C) in a way that a slurry is being formed, with the continuous phase having the appearance of a solution or an emulsion.
  • the total solids content of such solution or slurry formed as result of step (a) is in the range of from 20 to 75%, preferably 35 to 50%.
  • such solution or slurry has a pH value in the range of from 2.5 to 13, preferably from 7 to 12 and even more preferably at least 8 up to 12.
  • Mixing may be performed with mechanical support, for example shaking or stirring.
  • step (b) a spray-drying or spray granulation is performed, using a gas with an inlet temperature of at least 125°C.
  • Said gas hereinafter also being referred to as "hot gas”
  • hot gas may be nitrogen, a rare gas or preferably air.
  • most of the water used in step (a) will be removed, for example at least 55%, preferably at least 65% of the water. In one embodiment of the present invention, 99% of the water at most will be removed.
  • the aqueous slurry or aqueous solution according to step (a) may have a temperature in the range of from 15 to 95°C, preferably 20 to 90°C and even more preferably 50 to 90°C.
  • the average residence time of chelating agent (A) in step (b) is in the range of from 2 minutes to 4 hours, preferably from 30 minutes to 2 hours.
  • such aging may take in the range of from 2 hours to 24 hours at the temperature preferably higher than ambient temperature.
  • fines have a particles diameter of 30 ⁇ m or less, for example 1 to 30 ⁇ m.
  • step (b) 40 to 100% of the fines present in the respective material withdrawn at the end of step (b) are separated off.
  • step (c) 80 to 99% by weight of the fines are separated off, and the residual 1 to 20% are left in the respective powder or granule. It is tedious to try to remove the fines quantitatively.
  • step (c) of the inventive process so-called lumps or “overs” may be separated off from said powder or granules.
  • said lumps to be separated off are particles that have a minimum particle diameter of 1,000 ⁇ m, for example, 1,500 ⁇ m to 2 mm or even more. In a preferred embodiment, lumps are particles that have a minimum particle diameter of 1,250 ⁇ m or more, even more preferably 900 ⁇ m to 2 mm.
  • said lumps or overs have a minimum particle diameter of 250 ⁇ m or more, for example 250 to 1,000 ⁇ m.
  • Overs or lumps may be removed, e.g., with the help of a discharge screw or a rotary valve, usually together with desired product, and then classified.
  • Separating off lumps and fines may be performed in any order, consecutively or simultaneously.
  • the amount of powder or granule, respectively, other than fines and overs is in the range of from 55 to 70% by weight, referring to total amount of material removed at the end of step (b).
  • the lumps separated of in step (c) may be milled down to a smaller size, for example to maximum particle diameter of 500 ⁇ m, preferably to a maximum particle diameter of 400 ⁇ m.
  • the milling may be performed in any type of mills. Examples of particularly useful mills are jet mills, pin mills and bolting machines (German: Stiftmühlen). Further examples are roller mills and ball mills.
  • said fines from step (c) and milled lumps from step (c) are reintroduced into a spray-dryer or spray-granulator.
  • Such reintroducing may be performed by pneumatically transporting said fines milled lumps from step (c) into the spray tower or spray granulator, respectively, preferably through an extra opening rather than together with solution or slurry from step (a).
  • powders and granules may be obtained.
  • Such powders and granules have a particularly high bulk density (German: Schüttêt), for example 800 to 950 g/l, preferably 850 to 920 g/l and more preferably 875 to 910 g/l, determined according to DIN ISO 697-1984-01.
  • the term "in molecularly disperse form” implies that all or a vast majority, for example at least 80% of the particles of inventive powder and of inventive granules contain chelating agent (A) and alkali metal silicate (B) and (co)polymer (C).
  • the term “in molecularly disperse form” implies as well that chelating agent (A) and alkali metal silicate (B) and (co)polymer (C)are distributed over the diameter of the particle in an almost homogeneous way.
  • inventive powders are selected from powders having an average particle diameter in the range of from 1 ⁇ m to less than 0.1 mm.
  • Inventive cleaning agents may contain at least one bleaching agent and at least one inventive powder or at least one inventive granule. Inventive cleaning agents show a reduced tendency for yellowing and therefore have an extended shelve-life.
  • suitable peroxy compounds are sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy- ⁇ -naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1 ,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as free acid or as alkali metal salt, in particular as sodium salt, also sulfonylperoxy acids and cationic peroxy acids.
  • organic peracids such as peroxylauric acid, peroxystearic acid, peroxy- ⁇ -naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid
  • peroxy compound is selected from inorganic percarbonates, persulfates and perborates.
  • sodium percarbonates are 2 Na 2 CO 3 ⁇ 3 H 2 O 2 .
  • sodium perborate are (Na 2 [B(OH) 2 (O 2 )] 2 ), sometimes written as NaBO 2 ⁇ O 2 ⁇ 3H 2 O instead.
  • Most preferred peroxy compound is sodium percarbonate.
  • inventive cleaning agents may contain further ingredients such as one or more surfactants that may be selected from non-ionic, zwitterionic, cationic, and anionic surfactants.
  • Other ingredients that may be contained in inventive cleaning agents may be selected from bleach activators, bleach catalysts, corrosion inhibitors, sequestering agents other than chelating agent (A), enzymes, fragrances, dyestuffs, antifoams, and builders.
  • advantageous inventive cleaning agents are free from phosphate.
  • "Free from phosphate” should be understood in the context of the present invention, as meaning that the content of phosphate and polyphosphate is in sum in the range from 10 ppm to 0.2% by weight, determined by gravimetric methods and referring to the respective inventive cleaning agent.
  • Inventive cleaning agents may contain one or more surfactant, preferably one or more non-ionic surfactant.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II) in which the variables are defined as follows:
  • compounds of the general formula (II) may be block copolymers or random copolymers, preference being given to block copolymers.
  • hydroxyalkyl mixed ethers are compounds of the general formula (IV) in which the variables are defined as follows:
  • n and n are in the range from zero to 300, where the sum of n and m is at least one, preferably in the range of from 5 to 50.
  • m is in the range from 1 to 100 and n is in the range from 0 to 30.
  • Compounds of the general formula (II) and (III) may be block copolymers or random copolymers, preference being given to block copolymers.
  • nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C 4 -C 16 -alkyl polyglucosides and branched C 8 -C 14 -alkyl polyglycosides such as compounds of general average formula (V) are likewise suitable. wherein the variables are defined as follows:
  • surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.
  • amphoteric surfactants are those that bear a positive and a negative charge in the same molecule under use conditions.
  • Preferred examples of amphoteric surfactants are so-called betaine-surfactants.
  • Many examples of betaine-surfactants bear one quaternized nitrogen atom and one carboxylic acid group per molecule.
  • a particularly preferred example of amphoteric surfactants is cocamidopropyl betaine (lauramidopropyl betaine).
  • amine oxide surfactants are compounds of the general formula (VI) R 7 R 8 R 9 N ⁇ O (VI) wherein R 7 , R 8 and R 9 are selected independently from each other from aliphatic, cycloaliphatic or C 2 -C 4 -alkylene C 10 -C 20 -alkylamido moieties.
  • R 7 is selected from C 8 -C 20 -alkyl or C 2 -C 4 -alkylene C 10 -C 20 -alkylamido and R 8 and R 9 are both methyl.
  • a particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide.
  • a further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide.
  • Suitable anionic surfactants are alkali metal and ammonium salts of C 8 -C 18 -alkyl sulfates, of C 8 -C 18 -fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C 4 -C 12 -alkylphenols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), C 12 -C 18 sulfo fatty acid alkyl esters, for example of C 12 -C 18 sulfo fatty acid methyl esters, furthermore of C 12 -C 18 -alkylsulfonic acids and of C 10 -C 18 -alkylarylsulfonic acids.
  • Suitable anionic surfactants are soaps, for example the sodium or potassium salts of stearoic acid, oleic acid, palmitic acid, ether carboxylates, and alkylether phosphates.
  • laundry detergent compositions contain at least one anionic surfactant.
  • inventive cleaning agents that are determined to be used as laundry detergent compositions may contain 0.1 to 60 % by weight of at least one surfactant, selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.
  • inventive cleaning agents that are determined to be used for hard surface cleaning may contain 0.1 to 60 % by weight of at least one surfactant, selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.
  • inventive cleaning agents do not contain any anionic detergent.
  • Inventive cleaning agents may comprise one or more bleach activators, for example N-methylmorpholinium-acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N-methylmorpholinium-acetonitrile salts
  • DADHT 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine
  • nitrile quats trimethylammonium acetonitrile salts
  • TAED tetraacetylethylenediamine
  • TAED tetraacetylhexylenediamine
  • Inventive cleaning agents may comprise one or more builders, selected from organic and inorganic builders.
  • suitable inorganic builders are sodium sulfate or sodium carbonate or silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, in particular those of the formula ⁇ -Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 , and ⁇ -Na 2 Si 2 O 5 , also fatty acid sulfonates, ⁇ -hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid.
  • zinc salt can change.
  • zinc acetate or ZnCl 2 for preparing formulation according to the invention, but this converts at a pH of 8 or 9 in an aqueous environment to ZnO, Zn(OH) 2 or ZnO ⁇ aq, which can be present in non-complexed or in complexed form.
  • Zinc salt may be present in those inventive cleaning agents that are liquid at room temperature.
  • inventive cleaning agents zinc salts are preferably present in dissolved or in solid or in colloidal form.
  • inventive cleaning agents are free from heavy metals apart from zinc compounds.
  • this may be understood as meaning that inventive cleaning agents are free from those heavy metal compounds which do not act as bleach catalysts, in particular of compounds of iron and of bismuth.
  • "free from” in connection with heavy metal compounds is to be understood as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in sum in the range from 0 to 100 ppm, determined by the leach method and based on the solids content.
  • inventive cleaning agents has, apart from zinc, a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question. The fraction of zinc is thus not included.
  • heavy metals are deemed to be all metals with a specific density of at least 6 g/cm 3 with the exception of zinc.
  • the heavy metals are metals such as bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
  • inventive cleaning agents comprise no measurable fractions of bismuth compounds, i.e. for example less than 1 ppm.
  • the molecular weight of polymers (C.1) and (C.2) was determined GPC. Said measurements were performed at a pH value of 7.4 (phosphate buffer), stationary phase: cross-linked polyacrylate, mobile phase: water, pH value 7.4, phosphate buffer with 0.01 M NaN 3 .
  • a vessel was charged with 14.629 kg of an aqueous solution of (A.1) (40 % by weight). An amount of 124 g of a 48.5 % by weight aqueous solution of (B.1) and 246 g of a 49% by weight aqueous solution (C.1) was added. The spray liquor SL.1 so obtained was stirred vigorously and then heated to 70°C for 3 hours and subjected to spray granulation.
  • example detergent compositions for automatic dishwashing detergents can be formulated by mixing the respective components according to Table 3.
  • Table 3 Example detergent compositions for automatic dishwashing All amounts in g/sample ADW.1 ADW.2 ADW.3 either of Gr.1, Gr.2, Gr.3 or Gr.4 30 22.5 15 Protease 2.5 2.5 2.5 Amylase 1 1 1 n-C 18 H 37 -O(CH 2 CH 2 O) 9 H 5 5 5 5 Sodium percarbonate 10.5 10.5 10.5 TAED 4 4 4 Na 2 CO 3 19.5 19.5 19.5 Sodium citrate dihydrate 15 22.5 30 HEDP 0.5 0.5 0.5 0.5 ethoxylated polyethylenimine, 20 EO/NH group, M n : 30,000 g/mol optionally: 0.1 optionally: 0.1 optionally: 0.1 optionally: 0.1
  • detergent compositions for automatic dishwashing detergents can be formulated by mixing the respective components according to Table 4.
  • Table 4 Example detergent compositions for automatic dishwashing All amounts in g/sample ADW.1 ADW.2 ADW.3 either of C-Gr.5, C-Gr.6, C-Gr.7, C-Gr.8 or C-Gr.9 30 22.5 15 Protease 2.5 2.5 2.5 Amylase 1 1 1 n-C 18 H 37 -O(CH 2 CH 2 O) 9 H 5 5 5 5 5 Sodium percarbonate 10.5 10.5 10.5 TAED 4 4 4 Na 2 CO 3 19.5 19.5 19.5 Sodium citrate dihydrate 15 22.5 30 HEDP 0.5 0.5 0.5 ethoxylated polyethylenimine, 20 EO/NH group, M n : 30,000 g/mol optionally: 0.1 optionally: 0.1 optionally: 0.1 optionally: 0.1

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Claims (14)

  1. Procédé pour la préparation d'une poudre d'un granulé contenant
    (A) au moins un agent chélatant choisi parmi des sels de métal alcalin d'acide méthylglycinediacétique (MGDA) et de diacétate d'acide glutamique (GLDA) et d'acide iminodisuccinique (IDS),
    (B) au moins un silicate de métal alcalin, et
    (C) au moins un (co)polymère contenant un groupe acide carboxylique, partiellement neutralisé avec un alcali,
    en un rapport en poids de (A) : [(B) + (C)] allant de 20 : 1 jusqu'à 100 : 1,
    ladite poudre ou ledit granulé contenant au moins 75 % en poids d'agent chélatant (A),
    ledit procédé comprenant les étapes de
    (a) mélange de l'au moins un agent chélatant (A) et de l'au moins un silicate de métal alcalin (B) et de l'au moins un (co)polymère (C) en la présence d'eau,
    (b) élimination de la plupart de ladite eau par séchage par pulvérisation ou granulation par pulvérisation en utilisant un gaz avec une température d'entrée d'au moins 125 °C.
  2. Procédé selon la revendication 1, l'agent chélatant (A) étant choisi parmi le sel trisodique de MGDA et le sel tétrasodique de GLDA.
  3. Procédé selon la revendication 1 ou 2, ledit silicate de métal alcalin (B) étant le sel de sodium de verre d'eau.
  4. Procédé selon l'une quelconque des revendications précédentes, le (co)polymère (C) étant choisi parmi un poly(acide acrylique), des copolymères statistiques d'acide acrylique et d'anhydride maléique ou d'acide 2-acrylamido-2-méthylpropanesulfonique, chaque (co)polymère étant partiellement choisi avec un alcali.
  5. Procédé selon l'une quelconque des revendications précédentes, l'étape (b) étant réalisée avec une buse à deux fluides.
  6. Poudre ou granulé contenant
    (A) au moins un agent chélatant choisi parmi l'acide méthylglycinediacétique (MGDA) et le diacétate d'acide glutamique (GLDA) et l'acide iminodisuccinique (IDS) et leurs sels de métal alcalin respectifs,
    (B) au moins un silicate de métal alcalin, et
    (C) au moins un (co)polymère contenant un groupe acide carboxylique, partiellement neutralisé avec un alcali,
    en un rapport en poids de (A) : [(B) + (C)] allant de 20 : 1 jusqu'à 100 : 1,
    sous forme dispersée de manière moléculaire, au moins 80 % des particules de poudre et de granules contenant un agent chélatant (A) et un silicate de métal alcalin (B) et un (co)polymère (C), et (A), (B) et (C) étant distribués sur le diamètre des particules de manière presque homogène, et
    ladite poudre ou ledit granulé contenant au moins 75 % en poids d'agent chélatant (A).
  7. Poudre ou granulé selon la revendication 6 possédant une teneur en humidité résiduelle dans la plage allant de 1 à 20 % en poids.
  8. Poudre selon la revendication 6 ou 7 possédant un diamètre moyen de particule dans la plage allant de 1 µm à moins de 0,1 mm.
  9. Granulé selon la revendication 6 ou 7 possédant un diamètre moyen de particule dans la plage allant de 0,1 mm à 2 mm.
  10. Poudre ou granulé selon l'une quelconque des revendications 6 à 9, ledit silicate de métal alcalin étant le sel de sodium du verre d'eau correspondant.
  11. Poudre ou granulé selon l'une quelconque des revendications 6 à 10, l'agent chélatant (A) étant choisi parmi le sel trisodique de MGDA et le sel tétrasodique de GLDA.
  12. Poudre ou granulé selon l'une quelconque des revendications 6 à 11, ledit (co)polymère (C) étant choisi parmi un poly(acide acrylique), des copolymères statistiques d'acide acrylique avec l'anhydride maléique ou l'acide 2-acrylamido-2-méthylpropanesulfonique, chaque (co)polymère étant partiellement choisi avec un alcali.
  13. Utilisation d'une poudre ou d'un granulé selon l'une quelconque des revendications 6 à 12 pour la fabrication d'un agent de nettoyage pour des fibres ou des surfaces dures, ledit agent de nettoyage contenant au moins un composé de type peroxy choisi parmi des percarbonates, des persulfates et des perborates.
  14. Agent de nettoyage, contenant au moins un composé de type peroxy et au moins une poudre ou un granulé selon l'une quelconque des revendications 6 à 12.
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PL3822335T3 (pl) * 2019-11-15 2023-03-13 Basf Se Kompozycje czyszczące i ich zastosowanie
CN113999733B (zh) * 2021-12-03 2024-04-05 广州立白企业集团有限公司 一种颗粒组合物及洗碗机专用洗涤剂组合物
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US5837663A (en) 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
US8183410B2 (en) * 2008-04-01 2012-05-22 Conopco, Inc. Preparation of free flowing granules of methylglycine diacetic acid
GB2491619B (en) * 2011-06-09 2014-10-01 Pq Silicas Bv Builder granules and process for their preparation
WO2013160132A1 (fr) * 2012-04-25 2013-10-31 Basf Se Formulations solides et production et utilisation desdites formulations
WO2014037255A1 (fr) * 2012-09-07 2014-03-13 Basf Se Particules, procédé de fabrication et utilisation
MX2016010570A (es) * 2014-02-13 2016-11-29 Basf Se Polvo y granulo, proceso para fabricar dicho polvo y granulo, y sus usos.
WO2017220308A1 (fr) * 2016-06-20 2017-12-28 Basf Se Poudres et granulés et procédé de fabrication desdites poudres et desdits granulés

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